bottom technical area
The present invention relates to compounds for organic electronic components, organic electronic components using the same, and electronic devices thereof.
art background
Flat panel displays play a very important role in supporting an advanced Internet-based imaging information society and have shown rapid growth in recent years. In particular, organic electroluminescent devices (organic EL devices) that can operate at low voltages like fluorescent types have excellent viewing angles and contrast ratios and do not require backlighting compared to liquid crystal displays (LCDs), which are the mainstream flat panel devices. It can be thin and light and also has advantages in terms of power consumption. Furthermore, it draws attention as a next-generation display device due to its fast response speed and wide color reproduction gamut. Generally, an organic EL element is formed on a glass substrate in the order of an anode consisting of a transparent electrode, an organic thin film including a light-emitting region, and a metal electrode (cathode). In this case, the organic thin film includes a hole injection layer (HIL), a hole transport layer (HTL), an electron transport layer (ETL) or an electron injection layer (HIL) in addition to Emitting Light Layer (EML) and luminescent properties of the layer also include Electron Blocking Layer (EBL) or Hole Blocking Layer (HBL) and luminescence assisting layer. When an electric field is applied to an organic EL device with this structure, holes are injected from the anode, electrons are injected from the cathode, and the injected holes and electrons pass through the hole transport layer and the transport layer. of electrons, respectively, and recombine in the light-emitting layer to form a light-emitting exciton. The light-emitting excitons formed emit light during the transition to the ground state. At this time, in order to improve the efficiency and stability of the light-emitting state, a light-emitting dye (guest) is also doped in the light-emitting state. layer (host). In order to use such an organic electronic device in various display media, the lifetime of the element is more important than anything else, and various studies are being conducted to increase the lifetime of the organic electronic element. In particular, to improve the lifetime characteristics of organic electronic devices, various studies have been conducted on organic materials inserted into buffer layers such as hole transport layers and luminescence support layers. A hole transport layer with high uniformity and low crystallinity in thin layers. films while providing high hole transport properties from the anode to the organic layer.
It is necessary to develop a material for the hole injection layer and the hole transport layer that not only has stable properties against the Joule heat generated during the operation of the device, i.e., a high glass transition temperature, but also can delay the penetration and diffusion of metal oxide. Anode electrode (ITO), which is one of the reasons for shortening the life of organic electronic devices. In addition, the low glass transition temperature of the orifice transport layer material has been reported to greatly affect the lifetime of the device according to the property that the smoothness of the film surface is destroyed during conduction. Of the device. In addition, the vapor deposition method is the mainstream in the formation of OLED devices, and a material that can withstand this vapor deposition method for a long time is required, that is, a material with strong heat resistance.
In particular, the biggest challenge with organic light-emitting diodes is the increased panel size of mobile phones and tablets, and problems such as power consumption and service life need to be solved immediately.
However, as a material of the hole transport layer, it is difficult to simultaneously exceed the activation voltage and the service life. The reason is that in order to reduce the activation voltage, a material with excellent hole transport ability, that is, high hole mobility, in most cases an electron-rich planar structure. For example, naphthyl, fluorenyl, and phenanthrenyl, etc.
However, when the compound with the above structure is introduced into the hole transport material as a substituent, the mobility of holes is increased to a certain extent, which has a good effect on the lifetime, but if the amount of introduction is increased in the molecule to meet current industrial requirements Low-voltage drive target, the drive voltage is reduced, and low-voltage drives can be achieved, but the life characteristics deteriorate rapidly.
The reason for this is that in the case of excessive introduction of electron-rich planar structure molecules, the holes get trapped between the plate-like structures and stabilize when a constant current is applied continuously during lifetime evaluation. of the device, which reduces the mobility of the holes. and eventually increases. Driving a voltage to apply a constant current results in drastic degradation of device life. Expressed by the following formula.
(J=space charge limited current, ε=permittivity, μ=coefficient of mobility, θ=coefficient of charge trapping (free carriers/total carriers), V=voltage, d=thickness) due to trapping phenomenon The number of carriers decreases and the value of 8 decreases, so in a current-driven organic light-emitting device that requires a constant current, the drive voltage increases, which has a fatal effect on lifespan. Therefore, as mentioned above, the introduction of an electron-rich lamellar structure capable of increasing hole mobility beyond a certain amount has a negative effect on lifetime and is therefore less likely to occur. trigger voltage is reduced when using it.
Therefore, the present inventors confirmed that deuterium-substituted compounds exhibit many thermodynamic properties as compared with unsubstituted compounds, and among these thermodynamic properties, when an iridium compound is substituted with deuterium, the properties change according to the carbon difference. and hydrogen. , and the bond lengths of carbon and deuterium compared to compounds not substituted with deuterium, compounds composed of deuterium may have higher light efficiency due to the weakened intermolecular van der Waals force generated by shorter bond lengths.
The method of reducing the conduction voltage by deuterium substitution, that is, increasing the hole transport mobility of hole transport materials, has not been much researched at present, and the existing technology is based on substitution. deuterium to show that its effect rate has not changed. has not yet been reported. Furthermore, the general deuterium substitution method described above has the disadvantage that the substitution rate is difficult to control.
Detailed description of the invention resume
In order to solve the aforementioned problems in the prior art, in the present invention, deuterium is replaced with a long-lived amine compound in a specific ratio of 59% to 73%, thus completing a long-lived device. lifespan to achieve long-life devices, which is a desired property for organic electronic devices.
Therefore, an object of the present invention is to provide a deuterated compound in a specific ratio, an organic electronic component using the compound, and an electronic device thereof.
Technical solutions
The present invention provides a 59% to 73% deuterated compound represented by Formula 1.
In another aspect, the present invention provides a process for preparing the 59% to 73% deuterated compound represented by Formula 1.
In another aspect, the present invention provides organic electrical elements and electronic devices comprising the compound represented by formula 1.
invention effect
Using the compound according to the present invention, high light efficiency, low driving voltage and high heat resistance of the device can be achieved, and the color purity and service life of the device can be significantly improved.
100,200,300: Organic electronic components110: first electrode120: Cavity injection layer130: Hollow Transportation Act140: light-emitting layer150: electron transport law160: law of injection of electrons170: the second electrode160: electron transport law170: law of injection of electrons180: Reinforcement layer for light effect210: buffering220: Auxiliary luminescence layer320: The first layer of cavity injection330: The transport layer of the first hole340: the first luminous layer350: the first electron transport layer360: first layer of charge generation361: Second layer of charge generation420: Second cavity injection layer430: Second hole transport layer440: Second luminescent layer450: Second electron transport layer CGL: Charge generation layer ST1: First stack ST2: second stack
Detailed description
Next, some embodiments of the present invention will be described in detail. Furthermore, in the following description of the present invention, when a detailed description of the known functions and configurations incorporated herein may obscure the scope of the present invention, it will be omitted.
Expressions like first, second, A, B, (a), (b), etc. they may also be used here when describing components of the present invention. Each of these terms is not used to define the nature, order, or sequence of the corresponding component, but is only used to distinguish the corresponding component from other components. Note that if a component is described as "connected", "docked", or "connected" to another component, the component may be directly connected or connected to the other component, but the other component may be "connected", each component is "coupled" or "connected" to each other.
As used in the specification and the appended claims, unless otherwise indicated, the following are the meanings of the terms.
As used herein, unless otherwise indicated, the term "halogen" or "halogen" includes fluoro, bromo, chloro, or iodo.
Unless otherwise indicated, the term "alkyl" or "alkyl" as used herein has a single bond of 1 to 60 carbon atoms and refers to a saturated aliphatic functional group, including straight chain alkyl, branched alkyl, cycloalkane (cycloaliphatic) group, alkyl-substituted cycloalkyl or cycloalkyl-substituted alkyl.
Unless otherwise specified, the term "alkenyl" or "alkynyl" as used herein has, but is not limited to, double or triple bonds of 2 to 60 carbon atoms, and includes straight-chain or branched-chain groups.
Unless otherwise specified, the term "cycloalkyl" as used herein refers to, but is not limited to, a cycloalkyl group of 3 to 60 carbon atoms.
Unless otherwise specified, as used herein, the term "alkoxy", "alkoxy" or "alkoxy" refers to, but is not limited to, an oxy group attached to an alkyl group, and having 1 to 60 carbon atoms.
Unless otherwise indicated, the term "aryloxy" or "aryloxy" as used herein refers to, but is not limited to, an oxygen radical attached to an aryl group and having 6 to 60 carbon atoms.
Unless otherwise specified, the terms "aryl" and "arylene" used in the present invention have 6 to 60 carbon atoms, respectively, but are not limited thereto. In the present invention, aryl or arylene refers to monocyclic or polycyclic aromatic compounds, including aromatic rings formed by connecting adjacent substituents or participating in reactions.
For example, aryl can be phenyl, biphenyl, fluorenyl, or spirofluorenyl.
The prefix "aryl" or "ar" refers to a group substituted with an aryl. For example, arylalkyl can be an alkyl group substituted with an aryl group, an arylalkenyl group can be an alkenyl group substituted with an aryl group, and the substituted aryl group has the number of carbon atoms as defined herein.
When a prefix is named later, it also means that the substituents are listed in the order described first. For example, arylalkoxy refers to aryl-substituted alkoxy, alkoxycarbonyl refers to alkoxy-substituted carbonyl, arylcarbonylalkenyl also refers to arylcarbonyl-substituted alkenyl, where aryl. An ylcarbonyl group can be a carbonyl group substituted with an aryl group.
Unless otherwise indicated, the term "heterocyclic group" as used herein includes, but is not limited to, one or more heteroatoms, has 2 to 60 carbon atoms, includes any of the monocyclic or polycyclic rings, and may include heteroaliphatic and heteroaryl rings. In addition, a heterocyclic group can also be formed in combination with an adjacent group.
Unless otherwise specified, the term "heteroatom" as used herein represents at least one of N, O, S, P, or Si.
In addition, the term "heterocyclic group" can include rings that include SO2instead of a cycle made of carbon. For example, "heterocyclic group" includes the following compounds.
Unless otherwise indicated, the term "fluorenyl" or "fluorenylene" as used herein refers to a monovalent or divalent functional group in which R, R', and R" are hydrogen in the following structures, the term "substituted fluorenyl" or "substituted" fluorenylene" means that at least one of the substituents R, R', R'' is a substituent other than hydrogen, including groups in which R and R' are joined to form a spiro compound together with its attached carbon.
As used herein, the term "spiro compound" has a "spiro association", and a spiro association refers to a bond in which two rings share only one atom. At this point, the atoms shared by the two rings are called "spiro atoms", and these compounds are called "single spiro", "double spiro", and "triple spiro" depending on the number of spiro atoms in the compound.
Unless otherwise indicated, the term "aliphatic" as used herein refers to aliphatic hydrocarbons having from 1 to 60 carbon atoms, and the term "alicyclic" as used herein refers to aliphatic hydrocarbons having from 3 to 60 carbon atoms in the ring.
As used herein, unless otherwise indicated, the term "ring" refers to an aliphatic ring of 3 to 60 carbon atoms or an aromatic ring of 6 to 60 carbon atoms or a heterocyclic ring of 2 to 60 carbon atoms or fused rings formed by their combination, including saturated rings or unsaturated rings.
Other heterocompounds or heterogroups in addition to those described above include, but are not limited to, one or more heteroatoms.
Unless expressly stated herein, "substituted" in the term "substituted or unsubstituted" means replaced by one or more selected from deuterium, halogen, amino, nitrile, nitro, a C1-C20rent, in C1-C20alkoxy, C1-C20alkylamine group, a C1-C20Alkylthiophengruppe, in C6-C20Arylthiophengruppe, C2-C20alkenyl, C2-C20Alkynyl, C3-C20Cycloalkyl, at C6-C20arilo, c6-C20Aryl substituted with deuterium, a C8-C20Aralkenyl, silyl, boronyl, germanyl and C2-C20Heterocyclic groups, but not limited to these substituents.
Furthermore, the formulas used in the present invention have the same definitions as the substituents defined by the indices in the following formulas, unless otherwise clearly indicated.
Here, when a is an integer 0, the substituent R1does not exist when a is the integer 1, the only substituent R1Attached to any carbon atom constituting the benzene ring, when a is an integer of 2 or 3, the respective bonds are as follows, where R1They may be the same or different.When a is an integer from 4 to 6, the form of bond to the carbon atom in the benzene ring is the same and the hydrogen bonded to the carbon atom in the benzene ring is omitted.
As used herein, the term "deuterate" refers to a compound or group in which deuterium is present at 100 times or more its natural abundance level.
As used herein, the term "perdeuterated" refers to a compound or group in which all hydrogens have been replaced by deuterium. The term "deuterated" is synonymous with "100% deuterated".
As used herein, the term "deuteric acid" refers to a compound capable of ionizing to donate deuterium ions to a Bronsted base. As used herein, deuteric acid does not contain ionizable hydrogen.
Next, a compound according to one aspect of the present invention and an organic electric element including the compound will be described.
The present invention is a method in which the activation voltage can be reduced without introducing a plate-shaped molecular structure that adversely affects the lifetime, using a material with a good lifetime, and using a method for substituting deuterium in a proper ratio. Reduce drive voltage.
When it is replaced by deuterium, the zero point energy, that is, the energy of the ground state, decreases. As the deuterium-carbon bond length becomes shorter than the hydrogen-carbon bond length, so does the volume of the hard nucleus. of the molecule decreases so that the decrease in electrical susceptibility can be reduced. By weakening the interaction between the paper molecules, you can increase the volume of the film. This property reduces the crystallinity of the film, that is, it creates an amorphous state, and is generally very efficient in achieving the amorphous state, which is critical for increasing OLED lifetime and driving performance.
In addition, when a deuterium-substituted compound is used to form a film, the film is formed in a glassy amorphous state, which greatly affects the hole mobility of the film, and this glassy amorphous state can reduce the limit of grain by isotropic and uniform. properties, thus accelerating the flow of charges, that is, the mobility of the hole.
The present invention provides a 59% to 73% deuterated compound represented by Formula 1.
i:
1) right1y R2each independently as C1-C20rent and R1y R2they cannot be combined with each other to form a ring;
where R1y R2casco C1-C30Alkyl, more preferably C1-C24I rent,
2) right3y R4they are each independently the same or different from one another and each is independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro;6-C60aryl; fluorenyl; a C2-C60Heterocyclic groups including at least one O, N, S, Si or P heteroatom; fused ring groups of C3-C60aliphatic ring and a C6-C60aromatic ring; one C1-C50I rent; one C2-C20alkenyl; House2-C20alkynyl; House1-C30alkoxi; in C6-C30ariloxi y -L'-N(RIN)(Db); or, when a and b are 2 or more, plus adjacent R3or more R4can be joined to form a ring where R3y R4are aryl groups, may preferably be C6-C30Aryl, more preferably C6-C25Aryl groups such as phenylene, biphenyl, naphthalene, terphenyl, and the like.
where if r3y R4are heterocyclic groups, may preferably be C2-C30Heterocyclyl, more preferably C2C24Heterocykliske grupper, f.eks. pirazina, tiofeno, piridina, pirimidindol, 5-fenil-5H-pirimido[5,4-b]indol, quinazolina, benzoquinazolina, carbazol, dibenzoquinazolina, dibenzofurano, dibenzotiofeno, benzotiofeno, benzotiofeno, benzotiofeno, benzotiofeno, fenilfenotiazina, ETC.
where if r3y R4are fused ring groups, preferably may be fused ring groups of C3-C30aliphatic ring and a C6-C30Aromatic ring, more preferably a group of fused rings of C3-C24aliphatic ring and a C6-C24aromatic ring.
where if r3y R4are alkyl groups, may preferably be C1-C30Alkyl, more preferably C3-C24I rent
where if r3y R4are alkoxy groups, they may preferably be C1C24alkoxy.
where if r3y R4are aryloxy groups, may preferably be C6C24Yoshimoto.
where L' is selected from the group consisting of single bonds; one C6-C60arylene; fluorenylene; group of fused rings of C3-C60aliphatic ring and a C6-C60aromatic ring; one C2-C60heterocyclic group; where RINy Rbeach independently selected from the group consisting of C6-C60aryl; fluorenyl; fused ring group of C3-C60aliphatic ring and a C6-C60aromatic ring; one C2-C601. Heterocyclic group comprising at least one heteroatom in O, N, S, Si or P;
where if L' is an arylene group, it may preferably be C6-C30Arylene, more preferably C6-C25Arylene groups such as phenylene, biphenyl, naphthyl, terphenyl, and the like.
where if L' is a heterocyclic group, it may preferably be C2C30Heterocyclyl, more preferably C2C24Heterocykliske grupper, såsom pirazina, tiofeno, piridina, pirimidindol, 5-fenil-5H-pirimido[5,4-b]indol, quinazolina, benzoquinazolina, carbazol, di benzoquinazolina, dibenzofurano, benzotienopiuropirimen, benzotienopiuropirimen, benzotienopiuropirimen, benzotienopiuropirina hombres, osv.
Where if L' is a fused ring group, it may preferably be a fused ring group of C3-C30aliphatic ring and a C6-C30Aromatic ring, more preferably a group of fused rings of C3-C24aliphatic ring and a C6-C24aromatic ring.
where if rINy Rbare aryl groups, may preferably be C6-C30Aryl, more preferably C6-C25Aryl groups such as phenylene, biphenyl, naphthalene, terphenyl, and the like.
where if rINy Rbare fused ring groups, preferably may be fused ring groups of C3-C30aliphatic ring and a C6-C30Aromatic ring, more preferably a group of fused rings of C3-C24aliphatic ring and a C6-C24aromatic ring.
where if rINy Rbare heterocyclic groups, may preferably be C2C30Heterocyclyl, more preferably C2C24Heterocykliske grupper, såsom pirazina, tiofeno, piridina, pirimidindol, 5-fenil-5H-pirimido[5,4-b]indol, quinazolina, benzoquinazolina, carbazol, di benzoquinazolina, dibenzofurano, benzotienopiuropirimen, benzotienopiuropirimen, benzotienopiuropirimen, benzotienopiuropirina hombres, osv.
grande1, grande2Me too3each independently selected from the group consisting of single links; one C6-C60arylene; fluorenylene; group of fused rings of C3-C60aliphatic ring and a C6-C60aromatic ring; and a C2-C60heterocyclic group;
where if L1, grande2Me too3are arylene groups, they may preferably be C6-C30Arylene, more preferably C6-C25Arylene groups such as phenylene, biphenyl, naphthyl, terphenyl, and the like.
where if L1, grande2Me too3are heterocyclic groups, may preferably be C2C30Heterocyclyl, more preferably C2C24Heterocykliske grupper, såsom pirazina, tiofeno, piridina, pirimidindol, 5-fenil-5H-pirimido[5,4-b]indol, quinazolina, benzoquinazolina, carbazol, di benzoquinazolina, dibenzofurano, benzotienopiuropirimen, benzotienopiuropirimen, benzotienopiuropirimen, benzotienopiuropirina hombres, osv.
where if L1, grande2Me too3are fused ring groups, preferably may be fused ring groups of C3-C30aliphatic ring and a C6-C30Aromatic ring, more preferably a group of fused rings of C3-C24aliphatic ring and a C6-C24aromatic ring.
4) a is an integer from 0 to 4, b is an integer from 0 to 3,
5) Argon1and argon2each independently selected from the group consisting of C6-C60aryl; House2-C60Heterocyclic groups including at least one O, N, S, Si or P heteroatom; fused ring groups of C3-C60aliphatic ring and a C6-C60aromatic ring; one C1-C60I rent; one C2-C20alkenyl; House2-C20alkynyl; House1-C30alkoxi; in C6-C30ariloxi y -L'-N(RIN)(Db);
Where are they1and argon2are aryl groups, may preferably be C6-C30Aryl, more preferably C6-C25Aryl groups such as phenylene, biphenyl, naphthalene, terphenyl, and the like.
Where are they1and argon2are heterocyclic groups, may preferably be C2C30Heterocyclyl, more preferably C2C24Heterocykliske grupper, såsom pirazina, tiofeno, piridina, pirimidindol, 5-fenil-5H-pirimido[5,4-b]indol, quinazolina, benzoquinazolina, carbazol, di benzoquinazolina, dibenzofurano, benzotienopiuropirimen, benzotienopiuropirimen, benzotienopiuropirimen, benzotienopiuropirina hombres, osv.
Where are they1and argon2are fused ring groups, preferably may be fused ring groups of C3-C30aliphatic ring and a C6-C30Aromatic ring, more preferably a group of fused rings of C3-C24aliphatic ring and a C6-C24aromatic ring.
Where are they1and argon2are alkyl groups, may preferably be C1-C30Alkyl, more preferably C1-C24rent where they are1and argon2are alkoxy groups, they may preferably be C1C24alkoxy.
Where are they1and argon2are aryloxy groups, may preferably be C6C24Yoshimoto.
6) where aryl, arylene, heterocyclic, fluorenyl, fluorenylene, fused ring, alkyl, alkenyl, alkoxy and aryloxy may be substituted with one or more substituents selected from deuterium substitution; halogen; silane group; siloxane group; live group; germanium group; cyano group; nitro group; C.1-C20alkylthio; C.1-C20alkoxy; W1-C20I rent; C.2-C20alkenyl; W2-C20alkynyl; C6-C20arilo; C6-C20deuterium-substituted aryl; a fluorenyl group; C.2C20heterocyclic group; C.3-C20cycloalquil; c7-C20arylalkyl; and C.8-C20arylalkenyl and -L'-N(RIN)(Dbsubstituents can also join together to form saturated or unsaturated rings, where the term "ring" refers to C3-C60aliphatic ring or C6-C60aromatic ring or C2-C60A heterocyclic group or a fused ring formed by a combination thereof.
Also, formula 1 is represented by any of formulas 2 to 4
i:
1) right1, R2, R3, R4, grande1, grande2, grande3, argon2, a and b are the same ones defined in equation 1,
2) right5, R6, R7, R8y R9Same definition as R3In Formula 1,
3) c is an integer from 0 to 5, d is an integer from 0 to 3, e, f, and g are independently an integer from 0 to 4,
4) rightINselected from the group consisting of C1-C50I rent; one C6-C60aryl; fluorenyl; a C2-C601. Heterocyclic group comprising at least one O, N, S, Si or F heteroatom;
where if rINis aryl, preferably can be C6-C30Aryl, more preferably C6-C25Aryl groups such as phenylene, biphenyl, naphthalene, terphenyl, and the like.
where if rINis a heterocyclic group that can preferably be C2C30Heterocyclyl, more preferably C2C24Heterocykliske grupper, såsom pirazina, tiofeno, piridina, pirimidindol, 5-fenil-5H-pirimido[5,4-b]indol, quinazolina, benzoquinazolina, carbazol, di benzoquinazolina, dibenzofurano, benzotienopiuropirimen, benzotienopiuropirimen, benzotienopiuropirimen, benzotienopiuropirina hombres, osv.
5) y1it O, S o CR′R″,
6) where R' and R" are each selected independently of C6-C60aryl; fluorenyl; a C2-C60Heterocyclic groups including at least one O, N, S, Si or F heteroatom; fused ring groups of C3-C60aliphatic ring and a C6-C60aromatic ring and -L'-N(RIN)(Dbor R' and R" are joined to form C6-C60aromatic ring; fluorenyl; one C2-C60A heterocyclic group comprising at least one O, N, S, Si or F heteroatom; or a fused ring group of C3-C60aliphatic ring and a C6-C60aromatic ring;
where if R' and R" are aryl, they can preferably be C6-C30Aryl, more preferably C6-C25Aryl groups such as phenylene, biphenyl, naphthalene, terphenyl, and the like.
where if R' and R" are heterocyclic groups, they may preferably be C2C30Heterocyclyl, more preferably C2C24heterocyclic Group,
Where if R' and R" are fused ring groups, they may preferably be fused ring groups of C3-C30aliphatic ring and a C6-C30Aromatic ring, more preferably a group of fused rings of C3-C24aliphatic ring and a C6-C24aromatic ring.
7) donde L', RINy RbSame as defined in equation 1.
Additionally, Formula 1 is represented by any of Formulas 5 to 9.
i:
1) right1, R2, R3, R4, grande1, grande2, grande3, a and b are the same ones defined in equation 1,
2) right5, R6, R7, R8, R9, c, d, e, f, g e Y1same as defined in equations 2 to 4,
3) right1,2' y R3′ has the same definition as R3In Formula 1,
4) a' is an integer from 0 to 5, b' is an integer from 0 to 3, c' is an integer from 0 to 4,
5) y2is it O or S
Furthermore, Formula 1 is represented by any of the following compounds P-1 to P-42.
Furthermore, the present invention provides a method for preparing a 59%-73% deuterated compound represented by formula 1, comprising:
-
- (a) Dissolve the compound represented by formula 1 in perdeuterated benzene (benzene-D6);
- (b) Step to form the second reagent by adding deuterium-trifluoromethanesulfonic acid (CF3)3so3D) the first reagent;
- (c) reacting the second reagent at 80°C for 3 hours to 18 hours to perform the deuteration step;
- (d) Addition of Na quenching step2carbon monoxide3yo ding2After the reaction is complete, the other reactant is cooled to room temperature,
- (e) After concentrating the organic solvent in the second reagent, recrystallize with solvents of toluene and acetone to obtain the deuterated compound shown in formula 1.
In step (c), the deuteration reaction time may be from 3 hours to 18 hours, preferably 3 hours.
reference
The organic material layer may sequentially comprise a hole injection layer (120), a hole transport layer (130), the light-emitting layer (140), electron transport law (150), and the electron injection shell (160) at the first electrode (110). In this case, the rest of the layers except the emissive layer (140) cannot be sustained. It may also include a hole blocking layer, an electron blocking layer, a luminescent auxiliary layer (220), Bufferlaget (210) etc. and the electron transport shell (150) etc. Can be used as a hole blocking layer. (see
Furthermore, according to the embodiment of the present invention, the organic electrical element may further include a protective layer or a light efficiency enhancing layer (180The light efficiency enhancing layer can be formed on one of the two surfaces of the first electrode that is not in contact with the layer of organic material, or on one of the two surfaces of the second electrode that is not in contact with the organic material. organic material. layer.
The compound according to the embodiment of the present invention applied to the organic material layer can be used as a hole injection layer (120), the hollow transport layer (130), the auxiliary luminescence layer (220), auxiliary electron transport layer, electron transport layer (150), and the electron injection shell (160), the host or dopant of the light-emitting layer (140) or materials for the layer of amplification of light effects. Preferably e.g. the compound of formula A according to the present invention is used as a material for the luminescence supporting layer or the hole transporting layer.
The organic material layer may include 2 or more stacked layers, including a hole transport layer, a light-emitting layer, and an electron transport layer formed sequentially at the anode, and also includes a charge generation layer. formed between the 2 or more stacked layers. cape (see
Otherwise, even for the same kernel, its bandgap, electrical properties, interface properties, etc. can vary depending on where the substituents are linked, so the choice of the nucleus and the combination of linked sub-substituents are also important, especially long lifetime and high efficiency can be achieved simultaneously when the energy level and the T1 value of each layer of organic material and the unique properties of the material (flowability, interfacial properties, etc.) are optimally combined.
An organic electroluminescence device according to an embodiment of the present invention can be produced using a PVD (physical vapor deposition) method. For example, depositing a conductive metal or metal oxide or its alloy on the substrate to form an anode that forms a layer of organic material including a hole injection layer (120), the hollow transport layer (130), the light-emitting layer (140), electron transport law (150) and the electron injection shell (160) on it, can be done by depositing on it a material that can be used as a cathode.
In addition, the organic material layer in the present invention is formed by any of a spin coating method, a nozzle printing method, an inkjet printing method, a groove coating method, a coating method by immersion and a roll-to-roll method. . and the organic material layer provides an organic electronic element comprising the compound as an electron transport material.
As another specific example, the same or different types of compounds represented by formula 1 are mixed and used in the organic material layer.
Furthermore, the present invention provides a luminescence support layer composition comprising the compound represented by formula A and provides an organic electrical element comprising the luminescence support layer.
Furthermore, this invention provides the composition of the hole transport layer containing the compound represented by the formula (A) and the organic electronic device provided with this hole transport layer.
Furthermore, this invention provides the electronic equipment provided with the display device containing the organic electronic element. and a control unit for driving the display device;
On the other hand, the organic electric element is at least one of an organic electroluminescence device, an organic solar cell, an organic photoconductor, an organic transistor and a device for monochrome or white light illumination. At this point, electronic equipment may be current or future wired/wireless communication terminals, including mobile phones, personal digital assistants (PDAs), electronic dictionaries, point-to-multipoint (PMPs), remote controls, navigation devices, game consoles , several TVs and several computers.
Next, examples are given to describe in detail the synthesis example of the compound represented by the formula A according to the present invention and the production example of the electromechanical device according to the present invention, but the present invention is not limited to the following examples
Synthesis example 1
As shown in Reaction Scheme 1, the compound represented by formula 1 of the present invention (final product 1-1) was prepared by reacting Sub 1 with Sub 2.
The deuterated compound of the compound (final product 1-1) shown in formula 1 according to the present invention is obtained by dissolving all of the deuterated benzene (benzene-D)6), addition of deuterium-trifluoromethanesulfonic acid (CF3so3D), react at a temperature of 80°C for 3 hours to 18 hours, more preferably 3 hours.
1. Example of synthesis of P-2
(1) Synthesis of P 1-2
Sub 1-1 (10.5 g, 45.9 mmol), Sub 2-1 (22.3 g, 45.9 mmol), Pd2(dba)3 (1.3 g, 1.4 mmol), t -BuONa (8.8 g, 91.8 mmol) was placed in round-bottom flask, dissolved in anhydrous toluene (210 mL), then P(t-Bu) dissolved;3(50 wt% sol.) (1.11 mL, 2.8 mmol) and heated and stirred at 110 °C for ca. 4 hours. After TLC confirms the reaction is complete, cool to room temperature and extract with CH2claws2and water. The separated organic layer was dried with MgSO 44The resulting compound was purified on a silica gel column (hexane:CH2claws2=4:1) to obtain 25.8 g (yield: 83%) P1-2.
(2) Synthesis of P-2
Dissolve P 1-2 (15.0 g, 22.1 mmol) obtained in the above synthesis in perdeuterated benzene (C6command6(167,6 g, 1991,5 mmol) y FC3so3Add D (16.6 g, 110.6 mmol) and react at 80 °C for 3 h to generate a deuterated product. Take samples regularly, measure the degree of deuteration by LC-MS, after the deuterium exchange reaction is complete at the desired substitution rate, cool to room temperature, add Na to stop2carbon monoxide3yo ding2Or, concentrated organic solvent. Recrystallization using solvents of toluene and acetone gave 14.7 g (yield: 94%) of the deuterated compound P-2. The final mass was determined by LC-MS and confirmed to be 72.9% deuterated.
2. Example of synthesis of P-3
(1) Synthesis of P 1-3
Sub 1-3 (11,3 g, 49,4 mmol), Sub 2-3 (24,7 g, 49,4 mmol), Pd2(dba)3(1.4 g, 1.5 mmol), t-BuONa (9.5 g, 98.8 mmol) was placed in a round bottom flask, dissolved in anhydrous toluene (230 mL) and then P(t- Boo)3(50 wt% sol) (1.2 mL, 2.96 mmol) and heated and stirred at 110 °C for ca. 4 hours. After TLC confirms the reaction is complete, cool to room temperature and extract with CH2claws2and water. The separated organic layer was dried with MgSO 44The resulting compound was purified on a silica gel column (hexane:CH2claws2=4:1) to obtain 29.0 g (yield: 85%) P1-3.
(2) Synthesis of P-3
Dissolve P 1-3 (18.5 g, 26.7 mmol) obtained in the previous synthesis in perdeuterated benzene (C6command6(202,5 g, 2406,5 mmol) y CF3so3Add D (20.1 g, 133.7 mmol) and react at 80 °C for 3 h to form a deuterated product. Take samples regularly, measure the degree of deuteration by LC-MS, after the deuterium exchange reaction is complete at the desired substitution rate, cool to room temperature, add Na to stop2carbon monoxide3yo ding2Or, concentrated organic solvent. Recrystallization using solvents of toluene and acetone gave 18.4 g (yield: 96%) of the deuterated compound P-3. The final mass was determined by LC-MS and confirmed to be 70.2% deuterated.
3. Example of synthesis of P-6
(1) Synthesis of P 1-6
Sub 1-3 (9,9 g，43,3 mmol），Sub 2-6（15,1 g，43,3 mmol），Pd2(dba)3(1.2 g, 1.3 mmol), t-BuONa (8.3 g, 86.6 mmol) was placed in a round bottom flask, dissolved in anhydrous toluene (200 mL) and then P(t- Boo)3(50 wt% solution) (1.05 mL, 0.5 mmol) and heated and stirred at 110 °C for ca. 4 hours. After TLC confirms the reaction is complete, cool to room temperature and extract with CH2claws2and water. The separated organic layer was dried with MgSO 44The resulting compound was purified on a silica gel column (hexane:CH2claws2=4:1) gave 19.2 g (yield: 82%) of P1-6.
(2) Synthesis of P-6
Dissolve P 1-6 (19.2 g, 35.5 mmol) obtained in the above synthesis in perdeuterated benzene (C6command6(268,5 g, 3190,3 mmol) y CF3so3Add D (26.6 g, 177.2 mmol) and react at 80 °C for 3 h to generate a deuterated product. Take samples regularly, measure the degree of deuteration by LC-MS, after the deuterium exchange reaction is complete at the desired substitution rate, cool to room temperature, add Na to stop2carbon monoxide3yo ding2Or, concentrated organic solvent. Recrystallization using solvents of toluene and acetone gave 18.4 g (yield: 93%) of the deuterated compound P-6. The final mass was determined by LC-MS and confirmed to be 59.2% deuterated.
4. Example of synthesis of P-7
(1) Synthesis of P 1-7
Sub 1-1 (10,2 g, 44,6 mmol), Sub 2-7 (14,3 g, 44,6 mmol), Pd2(dba)3(1.2 g, 1.3 mmol), t-BuONa (8.6 g, 89.2 mmol) was placed in a round bottom flask, dissolved in anhydrous toluene (200 mL) and then P(t- Boo)3(50 wt% sol.) (1.1 mL, 2.7 mmol) and heated and stirred at 110 °C for ca. 4 hours. After TLC confirms the reaction is complete, cool to room temperature and extract with CH2claws2and water. The separated organic layer was dried with MgSO 44The resulting compound was purified on a silica gel column (hexane:CH2claws2=4:1) to obtain 20.6 g (yield: 90%) of P1-7.
(2) Synthesis of P-7
Dissolve P 1-7 (15.0 g, 29.2 mmol) obtained in the above synthesis in perdeuterated benzene (C6command6(221,2 g, 2628,1 mmol) y CF3so3D (21.9 g, 146 mmol) was added thereto, followed by reaction at 80°C for 3 hours to form a deuteride. Take samples regularly, measure the degree of deuteration by LC-MS, after the deuterium exchange reaction is complete at the desired substitution rate, cool to room temperature, add Na to stop2carbon monoxide3yo ding2Or, concentrated organic solvent. Recrystallization using solvents of toluene and acetone gave 14.8 g (yield: 95%) of the deuterated compound P-7. The final mass was determined by LC-MS and confirmed to be 64.5% deuterated.
Example of comparative synthesis 1
1. Comparative synthesis of compound A-1
Dissolve P 1-2 (10.8 g, 15.9 mmol) obtained in the previous synthesis in perdeuterated benzene (C6command6(120,7 g, 1433,9 mmol) y FC3so3D (12.0 g, 79.7 mmol) was added thereto, followed by reaction at a temperature of 50°C for 20 hours to form a deuteride. After the reaction was complete with the desired substitution ratio, it was cooled to room temperature and quenched by the addition of Na2carbon monoxide3yo ding2Or, concentrated organic solvent. Recrystallization was carried out using solvents of toluene and acetone to obtain 10.0 g (yield: 92%) of the deuterated compound A-1. The final mass was determined by LC-MS and confirmed to be 23.1% deuterated.
From the results of Comparative Synthesis Example 1, it can be seen that the conventionally known general deuterium replacement method has a long reaction time and the deuterium replacement rate is much lower than the production method, so which is difficult to control the replacement. rate. according to the present invention. In the production method of the present invention, the reaction time is shortened by reacting at a temperature higher than the conventional reaction temperature for 3 to 18 hours, more preferably 3 hours, and a deuterated compound can be obtained with a rate of improved replacement. .
Meanwhile, the FD-MS values of the compounds P-1 to P-42 of the present invention prepared according to the above Synthesis Examples are shown in Table 1.
Manufacturing Evaluation of Organic Electronic Components
Example 1 Blue organic light-emitting device (auxiliary light-emitting layer)
After vacuum deposition of 60 nm thick 2-TNATA on the ITO layer (anode) formed on the glass substrate to form a hole injection layer, 60 nm thick NPB is vacuum deposited on the hole injection layer to form a hole injection layer. hole transport layer. Then, the compound P-1 according to the present invention is vacuum deposited onto the hole transport layer to a thickness of 20 nm to form a light-emitting auxiliary layer, 9,10-bis(naphthalen-2 -il)anthracene as the main body and BD-052X (Idemitsu Kosan Co., Ltd. Co., Ltd.) was used as a dopant in a weight ratio of 96:4 to form a light-emitting layer with a 30 nm thickness in the light-emitting auxiliary layer. Subsequently, (1,1'-biphenyl-4-ol)bis(2-methyl-8-hydroxyquinoline)aluminum (hereinafter referred to as BAlq) was deposited under vacuum at a thickness of 10 nm to form a hole-blocking layer. , and the top layer that blocks the hole, bis(10-hydroxybenzo[h]quinoline) beryllium (hereinafter BeBq2) was deposited under vacuum with a thickness of 40 nm to form an electron transport layer. Then, LiF, which is an alkali metal halide, was deposited with a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited with a thickness of 150 nm to form a cathode, thus producing a organic electroluminescent device.
Example 2 to Example 20 Blue organic electroluminescence device (auxiliary luminescence layer)
An organic electroluminescent device was prepared in the same manner as in Example 1, except that the compound of the present invention described in Table 2 was used instead of the compound P-1 of the present invention as the emission support layer material. of light.
Comparative Example 1 and Comparative Example 2
An organic electroluminescent device was prepared in the same manner as in Example 1, except that Comparative Compound 1 or Comparative Compound 2 described in Table 2 was used instead of Compound P-1 of the present invention as the layer material. auxiliary light emission.
Electroluminescence (EL) characteristics, the lifetime of T95, were measured using PR-650 from Photoresearch by applying a direct DC voltage to the organic electroluminescent devices prepared in Examples 1 to 20, Comparative Example 1 and Comparative Example 2 of the present invention Measured at 500 cd/m using a lifetime measurement device manufactured by McScience2Standard gloss, the measurement results are shown in Table 2.
As can be seen from the results in Table 2, when the organic electroluminescent device material of the present invention is used as a light-emitting auxiliary layer material for the production of blue organic light-emitting devices, the lifetime of the emitting device of organic light device is. comparable to the use of Comparative Compound 1 or Comparative Compound 2 Compared with the Comparative Example, the electroluminescent device can be significantly improved. Compared to Comparative Compound 1, which was not substituted with deuterium, 45.7% of the total hydrogen in Comparative Compound 2 was substituted with deuterium, showing better device performance with drive voltage, efficiency, and improved lifetimes, and compared to Comparative Compound 2. In comparison, compounds of the present invention, in which 59% to 73% of the total hydrogen atom is replaced by deuterium, last longer than the resulting .
When substituted for deuterium, as the deuterium-carbon bond length becomes shorter than the hydrogen-carbon bond length, the volume of the hard molecular core decreases, so that electrical susceptibility can be reduced. Therefore, the effect of reducing the crystallinity of the thin film, that is, the amorphous state, can be achieved, and as a result, the mobility of holes can be improved.
It can be seen that especially the compounds of the present invention undergo deuteration at a substitution rate higher than the existing substitution rate of 59% to 73%, which increases the BDE (bond dissociation energy) as compared to the comparative compound, thus maximizing the structure. The binding stability of, as a result, increases the stability of the molecules in the device, resulting in excellent results in terms of longevity.
This suggests that although they have similar structures, the physical properties and properties of the compounds and unit results may differ significantly due to the rate of deuterium substitution.
In the case of the auxiliary luminescence layer, it is necessary to understand the relationship between the hole transporting layer and the luminescent (host) layer, and it is difficult for those skilled in the art to understand the reason for the auxiliary luminescence layer derived from using the compound of the present invention, even if similar nuclei are used, they exhibited characteristics.
In addition, in the above device manufacturing evaluation results, it is described that only the compound of the present invention is applied to the device characteristics of the luminescence supporting layer, but the compound of the present invention can also be apply to one layer. which can be coated with either a hole transport layer or a hole transport layer, layer and auxiliary luminescence layer both.
Although exemplary embodiments of the present invention have been described for illustrative purposes, those skilled in the art will appreciate that various modifications may be made without departing from the scope and spirit of the invention as set forth in the appended claims. Add and replace. Therefore, the embodiments described in the present invention are intended to illustrate the scope of the technical idea of the present invention, and the scope of the present invention is not limited by the embodiments. The scope of the present invention is interpreted on the basis of the appended claims, and all technical ideas included in the corresponding scope of the claims are to be understood as belonging to the present invention.
industrial applicability
According to the present invention, an organic device with excellent device characteristics of high luminance, high luminescence and long lifetime can be produced, which therefore has industrial applicability.